Method for producing bio-jet fuel and apparatus for producing bio-jet fuel

Abstract

The objective is to provide a method and apparatus for producing bio-jet fuel that can efficiently and stably produce bio-jet fuel using biomass such as sewage sludge and organic waste. [Solution] The present invention provides a method for producing bio-jet fuel, comprising: a carbonization step of carbonizing biomass such as sewage sludge and organic waste to produce carbonized material; a reforming gasification step of gasifying the carbonized material with water vapor and carbon dioxide to produce reformed gas; an olefin production step of contacting the reformed gas with a methanol synthesis catalyst and a mesopore catalyst to produce olefins having 2 to 4 carbon atoms; an oligomerization reaction step of oligomerizing the olefins to produce iso-oligomers having 6 to 16 carbon atoms; a hydrogenation step of hydrogenating the iso-oligomers to produce bio-jet fuel containing isoparaffin; and a step of separating and recovering metal-containing residue generated in the reforming gasification step and mixing it with the biomass.

Description

[Technical Field]

[0001] The present invention relates to a method for producing bio-jet fuel and an apparatus for producing bio-jet fuel. [Background technology]

[0002] Organic waste such as sewage sludge, peat, and industrial waste is discharged in large quantities as biomass waste, and its disposal and treatment are becoming environmental problems. Therefore, there is a growing need to reduce the volume of sewage sludge and organic waste, and to develop energy resource technologies such as methane fermentation and gasification power generation that utilize them. Until now, sewage sludge has generally been used as a combustion fuel or disposed of as waste in landfills. In recent years, technologies have been developed for pyrolysis gasification of sewage sludge using oxygen, air, and steam at high temperatures, as well as technologies for producing carbonized materials by carbonizing sewage sludge and technologies for using it as an alternative fuel for thermal power generation (Patent Documents 1-3, Non-Patent Documents 1-2).

[0003] Specifically, Patent Document 1 discloses a sewage sludge pyrolysis gasification power generation system that generates electricity using pyrolysis gas produced by pyrolyzing sewage sludge. Patent Document 2 discloses a method for producing carbonized material by heating sewage sludge or biomass containing sewage sludge to 250°C or higher while passing a heating gas through it to remove volatile components in the biomass, and then indirectly heating it to 400-500°C to carbonize it. Patent Document 3 discloses a method for converting sewage sludge into fuel, which involves drying the sewage sludge and then adding woody biomass to the dried sewage sludge to carbonize it and produce pyrolysis gas and carbonized material. Non-patent document 1 discloses a sewage sludge carbonization system in which sewage sludge, which has been dewatered to a moisture content of around 80%, is further dried and then fed into a carbonization furnace for carbonization treatment. Non-patent document 2 discloses a method for producing carbonized sewage sludge fuel, which involves dewatering sewage sludge, further drying it to a moisture content of 25%, and then heating and thermally decomposing it in a rotary kiln to produce carbonized material.

[0004] Furthermore, methods have been developed for producing reformed gas by directly reacting agricultural waste such as vegetation, wood, rice straw, and bagasse, as well as organic waste such as peat, construction timber, cotton, paper, and food waste with steam, oxygen, and air at high temperatures. Other methods include a direct reformed gas production method, and a two-stage gas production technology, which involves carbonizing biomass raw materials through dry distillation and then reacting the resulting carbonized material with steam to produce reformed gas. The reformed gas produced by these biomass gasification technologies is a mixed gas containing carbon monoxide (CO), hydrogen (H2), methane (CH4), ethane (C2H6), carbon dioxide (CO2), and other elements. Conventional uses of the reformed gas include fuel for gas engine power generation and hydrogen production using hydrogen extraction technology from the reformed gas (Patent Documents 4-6, Non-Patent Documents 3-5).

[0005] Specifically, Patent Document 4 discloses a reformed gas produced from biomass that can be used in gas engines and gas turbines. Patent Document 5 discloses purifying gas obtained from biomass gas and using the purified gas as fuel to drive a gas turbine. Patent Document 6 discloses obtaining carbonized material from biomass or organic waste as a raw material, further generating water gas by thermal decomposition with steam and air, and using this water gas as fuel for an internal combustion engine that facilitates daily start-up and shutdown operation. Non-Patent Documents 3 and 4 disclose technologies and challenges related to gasifying biomass for power generation. Non-Patent Document 5 discloses a technology for producing biogas in a reformed gasifier using woody biomass such as forest resources as a raw material, and further storing the hydrogen in this biogas in methylhexane for use in hydrogen stations and hydrogen power generation.

[0006] However, with conventional technology, the carbonization process generates not only low molecular weight fuel gas but also oily components and heavy components such as tar, which may cause significant burdens and obstacles to subsequent reformed gas and hydrogen production. Furthermore, in recent years, from the perspective of economic and environmental impact, there has been a demand for energy conservation in the reforming and gasification of the aforementioned carbides and hydrogen production, reduction of production costs for reformed gas and hydrogen, and reduction of emissions of greenhouse gases such as carbon dioxide caused by the consumption of external fuels such as heavy oil, kerosene, and electricity.

[0007] On the other hand, from the perspective of reducing emissions of greenhouse gases, carbon neutrality of jet fuel, particularly in the aviation industry, has become an important issue. Bio-jet fuel produced from biomass and other sources is attracting attention as a way to achieve such carbon neutrality (Patent Documents 7, 8). Patent documents 7 and 8 disclose methods for producing bio-jet fuel consisting of isomerized hydrocarbons with 7 to 14 carbon atoms by heating and catalytically modifying biomass-derived oil. However, these conventional methods for producing bio-jet fuel using biomass as a raw material were insufficient for producing bio-jet fuel efficiently and stably. [Prior art documents] [Patent Documents]

[0008] [Patent Document 1] Japanese Patent Publication No. 2002-256884 [Patent Document 2] Japanese Patent Publication No. 2007-84728 [Patent Document 3] Patent No. 3861093 [Patent Document 4] International Publication No. WO2008 / 050727 [Patent Document 5] Patent No. 4295793 [Patent Document 6] Japanese Patent Publication No. 2004-35837 [Patent Document 7] International Publication WO2023 / 085337 [Patent Document 8] International Publication WO2024 / 071264 [Non-Patent Document]

[0009] [Non-Patent Document 1] Shin Shimura, Tadaaki Kono, Makoto Kitabayashi, Kenji Shimizu, "Biomass Fuel Utilization of Sewage Sludge Peat," Electric Steelmaking, Vol. 78, No. 1, pp. 73-78 (2007) [Non-Patent Document 2] Takeshi Amari, Mizuho Tanaka, Yoichi Koga, Satoshi Okuno, Akira Tajima, "Manufacture of Sewage Sludge Peat Fuel and Its Application to Biomass Power Generation," Proceedings of the 16th Symposium on Environmental Engineering, JSME, pp. 151-153 (2006) [Non-Patent Document 3] Supervised by Masaru Ichikawa, "New Developments in Biomass Refinery Catalyst Technology," CM&C Publishing (2011), pp70-77, pp99-106 [Non-Patent Document 4] Kenichi Sasauchi, "Power Generation Utilization by Pyrolysis Gasification of Biomass," Journal of the Combustion Institute of Japan, Vol. 47, No. 139 (2005), pp. 31-39 [Non-Patent Document 5] Masaru Ichikawa, "New Developments in Hydrogen Energy Technology Utilizing Biomass Resources," Life and Environment, Vol. 61, No. 1 (2016), pp. 27-32 [Summary of the Invention] [Problems to be Solved by the Invention]

[0010] The present invention has been made in view of the problems of the prior art as described above, and provides a method and an apparatus for manufacturing biojet fuel that can efficiently and stably manufacture biojet fuel using biomass such as sewage sludge and organic waste. [Means for Solving the Problems]

[0011] The present invention relates to a method for producing biojet fuel, which includes a carbonization step of carbonizing biomass to produce a carbide, a reformed gasification step of subjecting the carbide, steam, and carbon dioxide to a gasification reaction to produce a reformed gas containing hydrogen, carbon monoxide, methane, and carbon dioxide, an olefin production step of contacting the reformed gas with a methanol synthesis catalyst and a mesoporous catalyst to produce olefins having 2 to 4 carbon atoms, an oligomerization reaction step of subjecting the olefins to an oligomerization reaction to produce iso-oligomers having 6 to 16 carbon atoms, a hydrogenation step of hydrogenating the iso-oligomers to produce isoparaffins and producing biojet fuel containing the isoparaffins, and a separation and recovery step of separating and recovering a metal-containing residue generated together with the reformed gas in the reformed gasification step from the reformed gas and mixing the recovered metal-containing residue with the biomass.

[0012] In the present invention, the metal-containing residue may contain at least one element selected from the group consisting of alkali metals and alkaline earth metals including sodium, potassium, lithium, calcium, magnesium, and barium, boron, aluminum, iron, and nickel.

[0013] In the present invention, the olefin production step may include a separation step of separating the reaction gas generated by contacting the reformed gas with a methanol synthesis catalyst and a mesoporous catalyst into a mixed gas containing carbon monoxide and methane and olefins having 2 to 4 carbon atoms.

[0014] In the present invention, the olefin production step may further include a shift reaction hydrogen production step of reacting carbon monoxide and methane in the reaction gas generated in the olefin production step with steam to produce hydrogen and carbon dioxide.

[0015] In the present invention, the carbon dioxide generated in the shift reaction hydrogen production step may be introduced into the reformed gasification step, and the hydrogen generated in the shift reaction hydrogen production step may be mixed with the reformed gas obtained from the reformed gasification step.

[0016] In the shift reaction hydrogen production process described above, the present invention may also use a shift reaction catalyst comprising at least one element selected from the group consisting of iron, ruthenium, nickel, copper, zinc, potassium, lithium, magnesium, chromium, cobalt, molybdenum, zirconia, titanium, cerium, lanthanum, and neodymium, and a porous oxide support.

[0017] In the present invention, the carbonization gas generated together with the carbide in the carbonization step may be burned and introduced into at least one of the following steps: the carbonization step, the reforming gasification step, the steam heat exchange step, the steam heat exchange step, the olefin production step, and the oligomerization reaction step.

[0018] In the present invention, the carbonization gas generated together with the carbide in the carbonization step may be burned and introduced into at least one of the following steps: the carbonization step, the reforming gasification step, the steam heat exchange step, the shift reaction hydrogen production step, the olefin production step, and the oligomerization reaction step.

[0019] In the present invention, the methanol synthesis catalyst may contain at least one element selected from the group consisting of copper, zinc, chromium, manganese, scandium, lithium, sodium, potassium, cesium, magnesium, barium, platinum, palladium, iridium, molybdenum, tungsten, vanadium, zirconium, hafnium, titanium, yttrium, cerium, and lanthanum, and a porous support.

[0020] In the present invention, the mesoporous catalyst may include a porous support made of a mesoporous zeolite and a mesoporous clay mineral.

[0021] In the present invention, in the olefin production step, a composite catalyst prepared by mixing the methanol synthesis catalyst and the mesopore catalyst is used, and the volume ratio of the methanol synthesis catalyst to the mesopore catalyst in the methanol synthesis catalyst may be 0.1 to 5.

[0022] The present invention relates to a bio-jet fuel production apparatus and comprises: a carbonization furnace that introduces biomass and produces carbides; a reforming gasifier that introduces the carbides obtained in the carbonization furnace and reacts them with steam and carbon dioxide to produce a reformed gas containing hydrogen, carbon monoxide, methane, and carbon dioxide; an olefin production facility that introduces the reformed gas obtained in the reforming gasifier and contacts it with a methanol synthesis catalyst and a mesopore catalyst to produce an olefin having 2 to 4 carbon atoms; an oligomerization reaction facility that introduces the olefin and reacts it with an oligomerization reaction to produce an isoparaffin having 6 to 16 carbon atoms; and a hydrogenation facility that introduces the isoparaffin obtained in the oligomerization reaction facility and hydrogenates it to obtain bio-jet fuel. The apparatus further comprises: a separation and recovery means for separating and recovering metal-containing residue generated together with the reformed gas in the reforming gasifier from the reformed gas; and a means for introducing the metal-containing residue recovered by the separation and recovery means into the biomass.

[0023] The present invention may further include a shift reaction facility that reacts carbon monoxide and methane in the reaction gas generated in the olefin production facility with water vapor to produce hydrogen and carbon dioxide.

[0024] In the present invention, the olefin production equipment may include separation means for separating the generated reaction gas into an olefin having 2 to 4 carbon atoms and a gas containing carbon monoxide and methane.

[0025] In the present invention, the shift reaction equipment may include a transfer means for transferring the generated carbon dioxide to the reforming gasification furnace.

[0026] In the present invention, a combustion device is provided for burning the carbonization gas discharged from the carbonization furnace, and the combustion device may include a supply means for supplying the burned gas as a heating gas to at least one of the carbonization furnace, the reforming gasification furnace, the olefin production equipment, the oligomerization reaction equipment, and the hydrogenation equipment.

[0027] In the present invention, a combustion device is provided for burning the carbonization gas discharged from the carbonization furnace, and the combustion device may include a supply means for supplying the burned gas as a heating gas to at least one of the carbonization furnace, the reforming gasification furnace, the olefin production equipment, the oligomerization reaction equipment, the hydrogenation equipment, and the shift reaction equipment. [Effects of the Invention]

[0028] According to the present invention, it is possible to provide a method and apparatus for producing bio-jet fuel that can efficiently and stably produce bio-jet fuel using biomass such as sewage sludge and organic waste. [Brief explanation of the drawing]

[0029] [Figure 1] Figure 1 is a schematic diagram showing an apparatus according to an embodiment of the present invention. [Modes for carrying out the invention]

[0030] The following describes embodiments of the bio-jet fuel manufacturing method and bio-jet fuel manufacturing apparatus (hereinafter also simply referred to as the manufacturing method and manufacturing apparatus) according to the present invention. In the specification, if a numerical range is indicated by "~", it means that the numbers before and after the range are included as the lower and upper limits (i.e., the range is between "greater than" and "less than or equal to").

[0031] (First embodiment: Method for producing bio-jet fuel) This embodiment describes a method for producing bio-jet fuel. The method for producing bio-jet fuel in this embodiment is: A method for producing bio-jet fuel comprising: a carbonization step of carbonizing biomass to produce carbides; a reforming gasification step of gasifying the carbides with water vapor and carbon dioxide to produce a reformed gas containing hydrogen, carbon monoxide, methane, and carbon dioxide; an olefin production step of contacting the reformed gas with a methanol synthesis catalyst and a mesopore catalyst to produce olefins having 2 to 4 carbon atoms; an oligomerization reaction step of oligomerizing the olefins to produce isoparaffins having 6 to 16 carbon atoms; and a hydrogenation step of hydrogenating the isoparaffins to obtain bio-jet fuel, wherein in the reforming gasification step, a metal-containing residue generated together with the reformed gas is separated from the reformed gas and recovered, and the recovered metal-containing residue is mixed with the biomass.

[0032] [biomass] The biomass used as a raw material in this embodiment will now be described. The biomass used in this embodiment refers to reusable organic resources derived from plants and animals, and is not particularly limited as long as it is not a fossil fuel such as petroleum. Examples include sewage sludge and organic waste. Sewage sludge generally refers to sewage sludge generated at sewage treatment facilities, etc. When used in the method of this embodiment, sewage sludge can be dewatered to adjust its moisture content to about 80%. In addition, sewage sludge generated at sewage treatment facilities, etc., is sometimes used for methane gas production through methane fermentation treatment, etc., but the method of this embodiment can use sewage sludge before or after methane fermentation treatment. Sewage sludge is usually dewatered to about 80% by mass, then crushed from a dewatered cake state, and may be further dried in a kiln dryer or the like to a moisture content of about 15% by mass to 30% by mass.

[0033] Examples of organic waste include forest timber such as cedar, pine, and bamboo; agricultural products and by-products such as rice straw and sugarcane; construction waste; industrial waste such as cotton and textile products; natural materials such as peat and driftwood; and crushed materials obtained by crushing these materials (hereinafter also referred to as raw material chips). The dimensions of the raw material chips are, for example, 5 to 100 mm. Organic waste may be used individually or in combination of two or more types.

[0034] Organic waste can also be dried in the same kiln dryer as the sewage sludge described above. In this case, it may be dried together with the sewage sludge, or it may be dried in a separate dryer and then mixed with the sewage sludge before being subjected to the carbonization process.

[0035] The biomass used as raw material in this embodiment may consist of sewage sludge and organic waste used individually, or both may be used together. In this embodiment, we will describe a case in which both sewage sludge and organic waste are used as biomass.

[0036] The waste heat gas discharged from such a dryer may be used in the manufacturing method of this embodiment, or it may be transferred to a system other than the manufacturing method and used as waste heat gas. Generally, dried sewage sludge contains relatively little carbon (for example, around 25-35% by mass), while organic waste contains a relatively large amount of carbon (for example, around 35-45% by mass). Therefore, by adding organic waste to sewage sludge, the amount of carbonized material obtained in the carbonization process can be increased. The mixing ratio of sewage sludge and organic waste can be adjusted as appropriate, but for example, the mass ratio of sewage sludge to organic waste can be in the range of 0.01 to 99.

[0037] Sewage sludge and organic waste may contain metals other than carbon, such as alkali metals and alkaline earth metals including sodium, potassium, lithium, cesium, calcium, magnesium, and barium, as well as boron, aluminum, iron, and nickel. These metals may also be added and mixed. The presence of these metals in the raw materials is preferable because it can promote carbonization in the carbonization process and generate reformed gas more efficiently in the reformed gasification process described later.

[0038] In this embodiment, in addition to adjusting the type and amount of sewage sludge and organic waste to include an appropriate amount of metal in the sewage sludge and organic waste, substances such as compounds that serve as sources of the aforementioned metals may be mixed with the sewage sludge and organic waste. As such a metal source, for example, metal-containing residue generated together with the reformed gas in the reforming gasification process may be used. Such metal-containing residue is residue separated and recovered from the reformed gas generated in the reforming gasification process.

[0039] The timing for mixing metal sources such as metal-containing residues with sewage sludge and organic waste can be either by adding a mixing step before the carbonization process, or by directly introducing the metal-containing residues and / or metal sources into the carbonization furnace. When mixing the metal sources before the carbonization process, for example, this could involve introducing them into a dryer that dries the sewage sludge and organic waste.

[0040] Methods for mixing metals with sewage sludge and organic waste include, for example, immersing the sewage sludge and organic waste in a solution obtained by dissolving a metal source such as metal-containing residue in a solvent such as water, alcohol, ether, or hydrocarbon, or spraying the solution onto the sewage sludge and organic waste to support the metals onto the sewage sludge and organic waste.

[0041] In the carbonization process of this embodiment, the inclusion of each of the aforementioned metals in the raw material promotes carbonization and increases the carbonization rate. The metal content in the metal-containing residue is typically around 0.01 to 100 g, or 0.1 to 50 g, per 1 kg of metal-containing residue. Furthermore, the weight ratio of metal-containing residue to the total of sewage sludge and organic waste (metal-containing residue ÷ sewage sludge + organic waste) can range from 0.01 to 0.99, or from 0.1 to 0.9. When the metal element content of the metal-containing residue and the weight ratio of the metal-containing residue to the total of sewage sludge and organic waste are within the aforementioned range, the carbonization rate and tar removal rate in the carbonization process of sewage sludge and organic waste tend to be superior. A higher carbonization rate makes it possible to increase the production volume of carbides, reformed gas, olefins (described later), isoparaffins, and the final product, bio-jet fuel. The metal content in this embodiment can be measured by ion chromatography, ICP emission spectrometry, and X-ray fluorescence analysis.

[0042] [Carbonization process] In this embodiment, a carbonization process is carried out to carbonize sewage sludge and organic waste to produce carbonized material. In the carbonization process, the raw materials, sewage sludge and organic waste, are heated in a low-oxygen or oxygen-free state to cause thermal decomposition. By thermally decomposing the raw materials, carbonized material and a carbonization gas containing low-molecular-weight fuel gas and heavy component fuels such as tar are produced. The carbonization process in this embodiment is carried out using a carbonization furnace.

[0043] As the carbonization furnace, one can be appropriately selected from known carbonization furnaces. Examples include carbonization furnaces equipped with external or internal heating devices, and carbonization furnaces equipped with heating material transfer devices such as screws and rotary furnaces.

[0044] The carbonization conditions for the carbonization process in this embodiment are as follows: The heating temperature in the carbonization process may be, for example, 200°C to 600°C, or 230°C to 500°C. The residence time in the carbonization process of this embodiment may be, for example, 5 minutes or more and 100 minutes or less, or 10 minutes or more and 60 minutes or less. By thermally decomposing the raw materials, sewage sludge and organic waste, at the above heating temperature and time, carbonized material can be efficiently obtained.

[0045] In the carbonization process of this embodiment, the raw materials may be supplied to the carbonization furnace continuously or intermittently. The metal-containing residue may also be supplied to the carbonization furnace continuously or intermittently.

[0046] [Combustion process of carbonized gas] In the manufacturing method of this embodiment, the carbonization gas generated together with the carbide in the carbonization process may be separated from the carbide, recovered, and burned to produce a high-temperature combustion gas. This combustion gas may be introduced into at least one of the following processes: the carbonization process, the reforming and gasification process described later, the olefin manufacturing process, the oligomerization reaction process, the hydrogenation process, or the process of heating steam by heat exchange, and used as waste heat gas for heating. Specifically, since the carbonized gas typically contains heavy fuel components such as tar, it is transferred to an air combustion furnace or the like, and burned at a temperature of, for example, 1000°C to 1200°C in an air atmosphere to obtain a high-temperature combustion gas from which the heavy fuel components have been removed. Because this combustion gas is at a high temperature, it can be transferred via piping equipment to each step of the manufacturing method of this embodiment, or to heating steps of other external systems such as dryers for sewage sludge and organic waste, and used as waste heat gas for heating each step.

[0047] By using the heat from combustion gases as waste heat gas and cascading it for heating in each step of the manufacturing method of this embodiment, heating can be performed without using external fuels (heavy oil, electricity, etc.), or with a smaller amount of combustion gas generated by burning external fuels in air than in conventional methods. Steps in the manufacturing method of this embodiment that can utilize such waste heat gas include, for example, drying of sewage sludge and organic waste, carbonization step (heating of carbonization furnace), reforming gasification step (heating of reforming gasification furnace), heat exchange step of steam for heating (steam heat exchange step), shift reaction hydrogen production step (heating of shift reaction hydrogen production equipment), olefin production step (olefin production equipment), oligomerization reaction step (oligomerization reaction equipment), and hydrogenation step (hydrogenation equipment). This will not only reduce the cost of gas production but also have the effect of mitigating global warming by reducing CO2 emissions.

[0048] [Reformed Gasification Process] The method of this embodiment includes a reforming gasification step in which the carbide obtained in the carbonization step is gasified in the presence of water vapor and carbon dioxide to produce a reformed gas containing hydrogen, carbon monoxide, methane, and carbon dioxide (hereinafter also referred to as H2, CO, CH4, and CO2). In the reforming gasification process of this embodiment, the following reactions occur. (1) Reaction of carbides with water vapor: C + H2O → H2 + CO (2) Reaction of carbide with carbon dioxide: C + CO2 → 2CO (3) Shift reaction: CO + H2O → CO2 + H2 (4) Methanation reaction: C + 2H2 → CH4

[0049] In the gasification temperature range (600°C to 10000°C) of the reformed gas process in this embodiment, the gasification reactions (1) and (2) between the carbide and water vapor and carbon dioxide are particularly promoted. In addition, reactions (3) and (4) occur incidentally, and reformed gas is produced. In this embodiment, the proportion of hydrogen in the reformed gas increases relatively when the gasification temperature is high. Furthermore, in the above-mentioned gasification reactions of carbides (1) and (2), by using carbon dioxide together with water vapor, it becomes possible to increase the amount of reformed gas produced by, for example, 1.2 to 2.5 times compared to reforming gas with water vapor alone.

[0050] The steam used in the reforming gasification process of this embodiment can be generated by heating tap water or other water, and this steam can be used. The carbon dioxide used in the reforming gasification process of this embodiment may be introduced into the reforming gasification furnace from a system separate from the manufacturing method of this embodiment, or carbon dioxide discharged from the shift reaction hydrogen production process described later may be introduced into the reforming gasification furnace.

[0051] The amount of carbide supplied to the reforming gasifier in the reforming gasification process of this embodiment can be adjusted as appropriate to efficiently produce reformed gas, but examples include 10 kg / h or more and 10,000 kg / h or less, or 50 kg / h or more and 5,000 kg / h or less. The amount of steam supplied to the reforming gasifier can be adjusted as needed, but for example, the amount of steam supplied per 1 kg / h of carbide supplied may be between 0.5 kg / h and 10 kg / h, or between 2 kg / h and 5 kg / h. The amount of carbon dioxide supplied to the reforming gasifier can be adjusted as needed, but for example, the amount of carbon dioxide supplied per 1 kg / h of carbide is 0.1 Nm³. 3 / h or more 10Nm 3 / h or less, or 0.5Nm 3 / h or more 5Nm 3 Examples include being less than or equal to / h. Furthermore, the ratio of the carbon dioxide supply to the total supply of water vapor and carbon dioxide (CO2 supply ÷ (water vapor supply + carbon dioxide supply)) can be, for example, 1% to 85% by volume, or 10% to 60% by volume.

[0052] In the reforming gasification process of the embodiment, the temperature of the reforming gasification furnace can be adjusted as appropriate to efficiently produce the reformed gas, but examples include 600°C to 1000°C, or 800°C to 900°C. As a heating means for the reforming gasification furnace, for example, the combustion gas obtained by burning the above-mentioned carbonization gas may be used as waste heat gas for heating.

[0053] Steam is supplied to the reforming gasification furnace after being heated in a heat exchanger, for example, by heating tap water to a range of 350°C to 800°C. When heating tap water using a heat exchanger or the like, waste heat gas from the reforming gasification furnace may be introduced into the heat exchanger for heating (steam heat exchange process). Furthermore, the waste heat gas from the heat exchanger that heated the tap water may be introduced into another process (for example, an olefin manufacturing process, an oligomerization reaction process, and a shift reaction hydrogen production process, etc.) and used for heating. In the bio-jet fuel manufacturing method of this embodiment, in addition to the economic effect of reducing the manufacturing costs of reformed gas, olefins, and bio-jet fuel by utilizing the waste heat gas for heating in other processes, it can also contribute to mitigating global warming by reducing carbon dioxide emissions.

[0054] The pressure in the reforming gasifier during the reforming gasification process can be adjusted as needed, but for example, it can be set to between 0.05 MPa and 0.5 MPa.

[0055] The reformed gas obtained in the reformed gasification process of this embodiment contains hydrogen (H2) and carbon monoxide (CO), and typically contains hydrogen (H2), carbon monoxide (CO), methane (CH4), and carbon dioxide (CO2). Examples of hydrogen content in reformed gas include 25% to 75% by volume, or 35% to 65% by volume. The range of carbon monoxide content in the reformed gas is, for example, 20% by volume or more and 60% by volume or 25% by volume or more and 50% by volume. The total content of hydrogen and carbon monoxide in the reformed gas can range from, for example, 60% to 100% by volume, or 70% to 90% by volume. The methane content in the reformed gas can be in the range of, for example, 0.1% by volume or more and 10% by volume or 0.5% by volume or more and 5% by volume. The range of carbon dioxide content in the reformed gas is, for example, 1% to 35% by volume, or 10% to 25% by volume. The content (volume %) of each component is the value at 25°C (room temperature) and 1 atmosphere.

[0056] [Separation and Recovery Process] In this embodiment, the metal-containing residue generated together with the reformed gas in the reformed gasification process is separated from the reformed gas and recovered, and the recovered metal-containing residue is mixed with the biomass in a separation and recovery step. In other words, in the reforming gasification process, the metals contained in the carbide remain as metal-containing residue, and this metal-containing residue is separated from the reformed gas and recovered. One recovery method is to separate the reformed gas containing the metal-containing residue discharged from the reforming gasification furnace from the metal-containing residue using a separation device such as a cyclone dust remover, and then recover the separated metal-containing residue. Such metal-containing residues can be recycled and supplied to the biomass receiving area (receiving equipment, etc.), the biomass mixing and drying stage (mixing equipment, dryer, etc.), and simultaneously with the carbonization process (inside the carbonization furnace) before being introduced into the carbonization process. As described above, by mixing them with sewage sludge and organic waste, the amount of waste discharged from the system of this manufacturing method can be reduced.

[0057] The metal-containing residue is recovered as residue from metals contained in sewage sludge and organic waste, and therefore contains metals contained in the raw materials, i.e., at least one element selected from the group consisting of alkali metals and alkaline earth metals such as sodium, potassium, lithium, calcium, magnesium, and barium, as well as boron, aluminum, iron, and nickel, which are metals contained in the aforementioned sewage sludge and organic waste.

[0058] The reformed gas from which metal-containing residues have been removed by the separation apparatus may be used not only for the production of bio-jet fuel, but also for other purposes, such as power generation in gasification power plants and hydrogen production.

[0059] [Gas purification process] The manufacturing method of this embodiment may include a gas purification step for purifying the reformed gas obtained in the reformed gasification step. In the gas purification step, it is preferable to remove components such as sulfur-containing components contained in the reformed gas. The reformed gas may contain sulfur-containing components such as hydrogen sulfide and COS derived from biomass raw materials. These sulfur-containing components can act as catalyst poisons and may reduce the catalytic activity and impair the stability in the olefin production step and oligomerization reaction step described later. Therefore, removing such sulfur-containing components can improve the stability of catalytic activity in each step.

[0060] For gas purification, for example, a known gas purifier can be used. Preferably, the purifier comprises a gas purification member in which at least one metal selected from the group consisting of Cu, Zn, Cr, Ce, Fe, Mo, and Co is supported on a porous carrier such as silica, alumina, or zeolite. By bringing such a gas purification member into contact with the reformed gas, sulfur-containing components bind to the metal and the porous carrier and are chemically removed from the reformed gas. The gas purifier is not limited to those that use chemical adsorption as described above, but may also be a gas purifier equipped with known gas adsorbents such as activated carbon or various zeolites. Furthermore, in addition to sulfur-containing components, gas purification may also remove nitrogen-containing components such as ammonia and NOx, and chlorine-containing components such as HCl.

[0061] [Olefin Manufacturing Process] The manufacturing method of this embodiment comprises an olefin manufacturing step in which the reformed gas is brought into contact with a methanol synthesis catalyst and a mesopore catalyst to produce an olefin having 2 to 4 carbon atoms. In the olefin manufacturing process, the reformed gas obtained in the reforming gasification process (which may also be reformed gas purified through a gas purification process) is first brought into contact with a methanol synthesis catalyst to produce methanol from H2, CO, CO2, and CH4 contained in the reformed gas. Furthermore, the methanol is brought into contact with a mesopore catalyst to produce a mixed gas of ethylene (C2H4), propylene (C3H6), and butene (C4H8), i.e., a gas containing olefins with 2 to 4 carbon atoms (hereinafter also referred to as C2-C4 olefins).

[0062] As a methanol synthesis catalyst, known methanol synthesis catalysts can be used, but examples include catalysts containing at least one element selected from the group consisting of copper, zinc, chromium, manganese, scandium, lithium, sodium, potassium, cesium, magnesium, barium, platinum, palladium, iridium, molybdenum, tungsten, vanadium, zirconium, hafnium, titanium, yttrium, cerium, and lanthanum (hereinafter also referred to as element (1)). These elements (1) may be supported on a carrier. Examples of carriers include porous carriers made of porous oxides such as silica and alumina. By selecting an appropriate element from the aforementioned element (1), and possibly multiple elements, the methanol production volume and selectivity can be improved. When using a methanol synthesis catalyst with a support, the amount of element (1) supported is, for example, 0.01 to 10% by mass, preferably 0.1 to 5% by mass. Here, the amount of element (1) supported is the ratio of the total mass of element (1) to the mass of the support.

[0063] Methanol synthesis catalysts can be produced by known methods. When producing a methanol synthesis catalyst in which element (1) is supported on a carrier, a solution containing element (1) may be supported on the carrier. The element (1) solution can be simultaneously or sequentially supported by methods such as immersion, dropwise addition, coating, or spraying within a predetermined temperature range. A specific example of a method for producing a methanol synthesis catalyst is to impregnate a support with a catalyst precursor containing element (1) dissolved in a solvent, and then perform an activation treatment to produce a methanol synthesis catalyst. Examples of catalyst precursors include salts of element (1). Examples of salts include hydrochloride salts, nitrates, formates, acetates, oxalic acid, citric acid, lactic acid, malate salts, and alkoxide salts. Examples of solvents include ethanol, methanol, ethers, and water. Methods for activation treatment include, for example, gradually increasing the temperature in the 250-600°C range in an oxygen-containing atmosphere, or gradually increasing the temperature in the 100-450°C range in a hydrogen gas atmosphere. In addition, as a hydrogen activation treatment, reduction treatment with reducing agents such as hydrazine or boron hydride may be performed. The selection of catalyst precursors, catalyst manufacturing processes, and activation conditions are not limited to these.

[0064] As mesopore catalysts, known catalysts can be used, but examples include mesopore catalysts containing mesopore zeolites such as ZSM-5, ZSM-11, SAPO-34, and erionite, which are characterized by a pore size of 0.36-0.55 nm x 0.50-0.56 nm, and mesointercalated clay minerals characterized by an interlayer distance of 0.35-0.56 nm. In this embodiment, it is preferable to treat the mesopore catalyst with phosphoric acid, boric acid, and a salt of at least one element selected from alkali metals and alkaline earth metals such as lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, and barium. This improves the selectivity and yield of olefins.

[0065] Mesopore catalysts can be manufactured by known methods. Specific manufacturing methods include, for example, dissolving a catalyst precursor containing the aforementioned elements in a solvent, impregnating a support with the resulting solution, and performing an activation process to obtain an activated mesopore catalyst. Examples of catalyst precursors include salts of the elements mentioned above. Examples of salts include hydrochloride salts, nitrates, and organic acid salts such as acetic acid, oxalic acid, citric acid, and lactic acid. Examples of solvents include ethanol, methanol, and water. Methods for activating and reactivating the catalyst include, for example, a method of gradually increasing the temperature in the range of 250 to 600°C in an oxygen-containing atmosphere, and a method of gradually increasing the temperature in the range of 100 to 450°C in a hydrogen gas atmosphere. The selection of catalyst precursors, the processes for manufacturing activated catalysts, and the activation treatment conditions are not limited to these.

[0066] The methanol synthesis catalyst and the mesopore catalyst can be used separately or as a composite catalyst by mixing the two. In this embodiment, it is preferable to use a composite catalyst in which a methanol synthesis catalyst and a mesopore catalyst are physically mixed, from the viewpoint of olefin yield and selectivity. When a composite catalyst is used, the amount of olefin produced and the olefin selectivity can be improved.

[0067] In a composite catalyst, the volume ratio of methanol synthesis catalyst to mesopore catalyst (methanol synthesis catalyst / mesopore catalyst volume ratio) can be, for example, 0.1 to 5 or 0.2 to 2. By keeping the methanol synthesis catalyst / mesopore catalyst volume ratio within the aforementioned range, methanol yield can be improved, as well as olefin selectivity and olefin production volume. The composite catalyst can be used in a fixed-bed, fluidized-bed, or slurry-type catalytic reactor in which it is dispersed in an organic solvent such as hexane, heptane, or octane. In particular, when installed in a slurry-type catalytic reactor, it improves the uniformity of the reaction layer temperature and enhances the stabilization of olefin production activity.

[0068] The reformed gas introduced into the olefin manufacturing process may be pressurized to a predetermined reaction pressure using a booster or other pressurizing device, and then continuously circulated and supplied. The reaction pressure of the reformed gas in the olefin manufacturing process is, for example, 0.1 to 5 MPa or 1 to 3.5 MPa. The reaction temperature is, for example, 200 to 500°C or 250 to 450°C. The airtime velocity of the reformed gas (SV: velocity of synthesis gas L / h / volume of catalyst L) is, for example, 1000 to 35000 h. -1 , or 3000~25000h -1 These are some examples. In the olefin manufacturing process of this embodiment, for example, an olefin selectivity of 65 to 95% and an olefin yield (STY: kg / L-cat / h) of 0.25 to 1.5 kg / L-cat / h can be obtained. Under the typical reaction conditions of this embodiment, the respective selectivity for olefins having 2 to 4 carbon atoms is 25 to 50% ethylene (C2), 25 to 45% propylene (C3), and 10 to 20% butene (C4).

[0069] In the olefin manufacturing process, the reaction gas may be cooled by an internal cooling device 56 to condense and separate the water generated in the reaction, and then discharged outside the system. In this case, improvements in olefin manufacturing efficiency and stabilization of catalyst activity can be ensured.

[0070] In addition to the C2-C4 olefins, the reaction gas generated in the olefin manufacturing process also contains light gases (carbon monoxide, methane, carbon dioxide). However, the distillation separator 52 separates these light gases, and the separated carbon monoxide and methane can be used in the shift reaction hydrogen production process.

[0071] [Oligomerization reaction process] The manufacturing method of this embodiment comprises an oligomerization reaction step in which the olefin is subjected to an oligomerization reaction to produce an isooligomer having 6 to 16 carbon atoms (hereinafter also referred to as a C6 to C16 isooligomer). In the oligomerization reaction step, the olefin generated in the olefin production step is heated and pressurized in the presence of a metal complex catalyst to produce isooligomers having 6 to 16 carbon atoms. Specifically, ethylene (C2), propylene (C3), and butene (C4) are isooligomerized to obtain C6 to C16 isooligomers.

[0072] The catalyst and reaction conditions in the oligomerization reaction step of this embodiment can be appropriately selected from known ones and within a known range and are not particularly limited. For example, the C6-C16 isooligomers can be obtained in a reactor under heating and pressurizing conditions such as 120-250°C and 2-5 MPa in the presence of a metal complex catalyst containing metals such as Co, Ti, Zr, and Al. In this embodiment, the light olefins with 2 to 5 carbon atoms that are generated simultaneously with the isooligomers in the oligomerization reaction step may be separated from the isooligomers using separation and recovery means such as a distiller, recovered, and returned to the oligomerization reaction step. By recycling these recovered light olefins back into the oligomerization reaction step, the production volume and yield of the target isooligomers with 6 to 16 carbon atoms can be improved.

[0073] [Hydrogenation process] The manufacturing method of this embodiment includes a hydrogenation step in which the isooligomer is hydrogenated to produce isoparaffin, and biojet fuel containing the isoparaffin is produced. In the hydrogenation step, the isooligomers produced in the oligomerization reaction step are hydrogenated to produce isoparaffins having 6 to 16 carbon atoms. The catalyst and reaction conditions in the hydrogenation step of this embodiment can be appropriately selected from known ones and within a range and are not particularly limited, but for example, in the presence of a precious metal catalyst containing platinum, palladium, iridium, etc., the C6 to C16 isooligomers are hydrogenated in a reactor under reaction conditions such as 250 to 350°C and 1 to 5 MPa to produce C6 to C16 isoparaffins. It is preferable that such isoparaffins are produced with a conversion rate of 85 to 90%. Such C6 to C16 isoparaffins are used as biojet fuel.

[0074] [Bio-jet fuel] The bio-jet fuel produced by the manufacturing method of this embodiment is an isoparaffin having 6 to 16 carbon atoms.

[0075] In the manufacturing method of this embodiment, the carbonization gas generated together with the carbide in the carbonization step may be burned and introduced into at least one of the following steps: the carbonization step, the reforming gasification step, the steam heat exchange step, the olefin production step, and the oligomerization reaction step. In this way, by recycling the heat and products generated within the system, such as using the carbonization gas as waste heat gas in each process, or using the metal-containing residue generated in the reforming gasification process to mix with the raw materials, it is possible to reduce emissions outside the system and mitigate the environmental burden.

[0076] In the bio-jet fuel manufacturing method of this embodiment, the yield of carbides can be increased by using metal-containing residue in the carbonization process. Furthermore, in the reforming gasification process, the yield of reformed gas can be increased by using carbon dioxide together with water vapor to perform mixed reforming gasification of the carbides. As a result, the yield of iso-oligomers with 6 to 16 carbon atoms obtained by oligomerizing olefins with 2 to 4 carbon atoms for bio-jet fuel, and isoparaffins obtained by hydrogenating the iso-oligomers, can be increased, which in turn reduces the manufacturing cost of bio-jet fuel and enables efficient bio-jet fuel production.

[0077] (Second embodiment: Method for producing bio-jet fuel) The bio-jet fuel manufacturing method of this embodiment is a bio-jet fuel manufacturing method that is similar to the bio-jet fuel manufacturing method shown in the first embodiment above, and further comprises a shift reaction hydrogen manufacturing step in which carbon monoxide and methane in the reaction gas generated in the olefin manufacturing step are reacted with water vapor to produce hydrogen and carbon dioxide.

[0078] [Shift reaction hydrogen production process] The manufacturing method of this embodiment may include a shift reaction hydrogen production step in which carbon monoxide and methane in the reaction gas generated in the olefin production step are reacted with water vapor to produce hydrogen and carbon dioxide. In the shift reaction hydrogen production process, a shift reaction (reaction 5 below) and a methane reforming reaction (reaction 6 below) are carried out to produce a mixed gas containing hydrogen and carbon dioxide. (5) Shift reaction: CO + H2O → CO2 + H2 (6) Methane reforming reaction: CH4 + 2H2O = 4H2 + CO2

[0079] In the manufacturing method of this embodiment, the light gases (carbon monoxide, methane, and carbon dioxide) that are separated from and recovered from the olefins generated in the olefin manufacturing process are introduced into the shift reaction hydrogen manufacturing process. By contacting such light gas with a shift reaction hydrogen production catalyst in the presence of water vapor, a mixed gas containing hydrogen and carbon dioxide is produced through the shift reaction and methane reforming reaction.

[0080] In the shift reaction hydrogen production process of this embodiment, a mixed gas consisting of hydrogen and carbon dioxide can be efficiently produced at a relatively low temperature by carrying out a shift reaction and a methane reforming reaction in the presence of a shift reaction hydrogen production catalyst.

[0081] Examples of shift reaction hydrogen production catalysts include those comprising at least one element selected from iron, ruthenium, nickel, copper, zinc, potassium, lithium, magnesium, chromium, cobalt, molybdenum, zirconia, titanium, cerium, lanthanum, and neodymium, and a porous oxide support. Any of these elements can be selected, but examples include composite catalysts containing one or more elements that act as catalysts for the shift reaction, such as lithium, magnesium, chromium, copper, zinc, potassium, etc., and one or more elements that act as catalysts for the methane reforming reaction, such as iron, ruthenium, nickel, cobalt, molybdenum, zirconia, titanium, cerium, lanthanum, neodymium, etc. As the support material, it can be appropriately selected from known catalyst supports, but examples include ceramics containing alumina, magnesium oxide, silicon oxide, etc., and porous oxides such as titanium oxide.

[0082] In the shift reaction hydrogen production process of this embodiment, the high-temperature combustion gas obtained in the carbonization gas combustion process described above may be introduced and used as waste heat gas for heating.

[0083] The processing conditions for the shift reaction in this embodiment are as follows: The heating temperature may be in the range of, for example, 250°C to 600°C, or 300°C to 450°C. The pressure in the shift reaction hydrogen production process of this embodiment may be, for example, 0.05 MPa to 5 MPa, or 0.09 MPa to 1 MPa. The residence time in the shift reaction hydrogen production process of this embodiment may be, for example, 1 minute or more and 100 minutes or less, or 5 minutes or more and 50 minutes or less. Furthermore, the gas hourly space velocity (GHSV) of the reformed gas relative to the catalyst is, for example, 100-5000 h -1 , or 500-3000h -1 These are some examples. By performing the shift reaction hydrogen production process under the above reaction conditions, a mixed gas containing high concentrations of hydrogen and carbon dioxide can be obtained more efficiently.

[0084] As described above, the shift reaction hydrogen production process generates carbon dioxide along with hydrogen, but this generated carbon dioxide may be separated from the hydrogen and introduced into the reforming gasification process. The process of separating hydrogen and carbon dioxide can be carried out in a hydrogen separation step that follows the shift reaction hydrogen production step.

[0085] The obtained hydrogen may be compressed under high pressure to become a compressed gas, or it may be cooled and liquefied. The separated carbon dioxide can be transferred by a transfer facility to the reforming gasification process and recycled as carbon dioxide used in the reforming gasification process.

[0086] [Hydrogen separation process] In this embodiment, a hydrogen separation step may be included. In the hydrogen separation process of this embodiment, a mixed gas containing high concentrations of hydrogen and carbon dioxide obtained in the shift reaction hydrogen production process is separated into hydrogen and carbon dioxide using a gas separation and purification apparatus or the like as a gas separation and purification means to obtain hydrogen. This hydrogen may be stored in a hydrogen holder or the like. Alternatively, the hydrogen may be mixed with reformed gas to adjust the concentration and supplied to the olefin production process. Examples of gas separation and purification methods include PSA type gas separators and ceramic membrane type gas separators. Either one of these gas separators may be used, or both may be used.

[0087] When the hydrogen obtained in the shift reaction hydrogen production process of this embodiment is supplied as a mixed gas to the olefin production process, the amount of olefin produced and the olefin production selectivity in the olefin production process can be significantly improved by adjusting the volume ratio of H2 / CO in the mixed gas to, for example, 1 to 3 or 1.5 to 2.5.

[0088] In the manufacturing method of this embodiment, a water electrolysis step using a water electrolysis facility may be provided to obtain the hydrogen necessary to adjust the H2 / CO gas ratio of the reformed gas supplied to the olefin manufacturing process. Commercial electricity can be used as the power source for such water electrolysis facility, but in order to reduce CO2 emissions from the system in the bio-jet fuel manufacturing method of this embodiment, electricity obtained from renewable energy sources such as solar and wind power generation or nuclear reactor power generation may also be used.

[0089] In the manufacturing method of this embodiment, all the same advantages as in the manufacturing method of the first embodiment are obtained, and furthermore, the following advantages are obtained by including a shift reaction hydrogen production step. In other words, by introducing the carbon dioxide generated in the shift reaction hydrogen production process into the reforming gasification process, the yield of reformed gas generated in the reforming gasification process can be increased. As a result, the production cost of bio-jet fuel can be reduced, and bio-jet fuel can be produced efficiently.

[0090] Furthermore, in the manufacturing method of this embodiment, the carbonization gas generated together with the carbide in the carbonization process may be burned to generate combustion gas, and this combustion gas may be used as a heat source in at least one of the following steps: the carbonization process, the reforming gasification process, the steam heat exchange process, the shift reaction hydrogen production process, the olefin production process, and the oligomerization reaction process. In this way, by recycling combustion gases and metal-containing residues generated within the system, such as using the carbonization gas as a heat source in each process, or recycling and mixing the metal-containing residue generated in the reforming gasification process with biomass raw materials to improve the carbonization rate of carbides, the yield of reformed gas can be improved. As a result, in addition to increasing the production yield of bio-jet fuel, production costs can be reduced.

[0091] (Third embodiment: Bio-jet fuel production apparatus) The bio-jet fuel production apparatus of this embodiment (hereinafter also simply referred to as the production apparatus) is shown with reference to Figure 1. The manufacturing apparatus 100 of this embodiment includes a carbonization furnace 20 that introduces biomass 1 (sewage sludge and organic waste) and produces carbonized material, a reforming gasifier 30 that introduces the carbonized material 2 obtained in the carbonization furnace 20 and performs a mixed gasification reaction with steam and carbon dioxide to produce a reformed gas containing hydrogen, carbon monoxide, methane, and carbon dioxide, an olefin manufacturing facility 50 that introduces the reformed gas obtained in the reforming gasifier 30 and brings it into contact with a methanol synthesis catalyst and a mesopore catalyst to produce olefins having 2 to 4 carbon atoms, and an oligo- This bio-jet fuel production apparatus comprises an oligomer reaction equipment 42 for producing iso-oligomers by a merization reaction, a distillation purification equipment 43 for introducing the iso-oligomers and distilling and separating the iso-oligomers having 6 to 16 carbon atoms, a light olefin recycling piping 45 for recycling and supplying residual light olefins (C2 to C5 olefins) to the oligomerization reaction equipment 42, and a hydrogenation equipment 44 for introducing the C6 to C16 iso-oligomers and hydrogenating them to obtain bio-jet fuel 90 consisting of isoparaines having 6 to 16 carbon atoms.

[0092] (Bio-jet fuel manufacturing facilities) A bio-jet fuel production apparatus 100 for producing bio-jet fuel according to this embodiment, as shown in Figure 1, will be described. First, the manufacturing apparatus of this embodiment, as equipment for carbonizing biomass, includes a biomass receiver 11 that receives biomass 1 supplied from an external source, and a rotary kiln dryer 12 (dryer) that dries the biomass 1 received by the biomass receiver 11. The biomass receiver 11 is equipped with a biomass supply device 91 that supplies biomass 1 into the receiver 11, and a biomass supply amount adjustment means 80 that supplies biomass 1 from the receiver 11 to the dryer 12. The biomass supply amount adjustment means 80 is equipped with means for adjusting the amount of biomass 1 supplied to the dryer 12 and for measuring its moisture content. The dryer 12 is connected to the carbonization furnace 20, and the system is configured so that the dried biomass 1 from the dryer 12 is transferred to the carbonization furnace 20.

[0093] The carbonization furnace 20 is equipped with a transfer device such as a screw-type biomass transfer equipment and a heating section (not shown) that uses combustion gas as a heat source via a combustion gas pipe 72. The carbonization furnace 20 is equipped with a lower outlet for discharging the generated carbonized material 2 and an upper outlet for discharging the carbonization gas generated in the carbonization furnace 20. An air combustion furnace 60 is connected to the upper outlet via piping. A carbonized material supply pipe is connected to the lower outlet, and the carbonized material can be fed into the reforming gasification furnace 30 via a carbonized material supply rate regulator 81 and a carbonized material supply device 92 provided in the carbonized material supply pipe.

[0094] The air combustion furnace 60 is configured to generate high-temperature combustion gas 6 by burning the carbonization gas 5 (containing tar) generated in the carbonization furnace 20 with air from an air blower 41.

[0095] Next, we will describe a reforming gasifier 30 that generates a reformed gas containing hydrogen, carbon monoxide, methane, and carbon dioxide by gasifying carbides with water vapor and carbon dioxide. The reforming gasifier 30, which performs reforming gasification, is configured to produce reformed gas 8 (a mixed gas of H2, CO, CH4, and CO2) by gasifying carbides 2 together with steam 7 and carbon dioxide 9. The reforming gasifier 30 comprises an inner cylinder 30a and an outer cylinder 30b surrounding the inner cylinder. Carbide material 2 is contained within the inner cylinder 30a. A combustion gas pipe (reforming gasifier) ​​73 from the air fuel furnace 60 is connected to the gap between the inner cylinder 30a and the outer cylinder 30b, and the combustion gas for heating is supplied via the combustion gas pipe 73. The inner cylinder 30a is heated by the combustion gas, and the heat from the inner cylinder 30a heats the carbide material, water vapor, and carbon dioxide, causing the reforming gasification to proceed.

[0096] The reforming gasifier 30 is connected to a steam supply pipe 33 that supplies steam to the interior and a CO2 supply pipe 32 that supplies carbon dioxide. A CO2 supply amount regulator 83 is provided in the CO2 supply pipe 32 to adjust the amount of CO2 supplied to the reforming gasifier 30. The steam supply piping is equipped with a steam heat exchanger 31 and a steam supply rate regulator 84 to adjust the temperature and amount of steam supplied to the reforming gasifier 30.

[0097] The manufacturing apparatus 100 of this embodiment includes a separation and recovery means for separating and recovering metal-containing residue generated together with the reformed gas in the reformed gasification furnace 30, and an introduction means for introducing the metal-containing residue recovered by the separation and recovery means into the biomass introduced into the carbonization furnace 20. Specifically, a reformed gas piping 35 is connected to the top of the reformed gasification furnace 30, which discharges the reformed gas generated therethrough via a reformed gas supply device 93, and is configured to transfer the reformed gas to a dust collector 34. The dust collector 34 is connected via piping to a gas purifier 36, a reformed gas supply rate regulator 86, a gas mixing and adjusting unit 89, and a booster gas circulation unit 88, and is configured to introduce the reformed gas into the olefin manufacturing equipment 50. The gas purifier 36 is configured to remove sulfur-containing and chlorine-containing components from the reformed gas, and known gas adsorbents such as those described above are used. Furthermore, the reformed gas discharged from the dust collector 34 is pressurized by a booster gas circulation system 88, such as a booster, to the reaction pressure required within the olefin manufacturing facility 50.

[0098] The dust collector 34 is equipped with a metal-containing residue separation and recovery equipment 94 that separates and recovers metal-containing residue contained in the reformed gas. A metal-containing residue receiver 38 for storing the metal-containing residue after separation and recovery in the dust collector 34 is connected to the dust collector 34 via a metal-containing residue discharge pipe 39. A metal-containing residue supply equipment 37 is connected to the metal-containing residue receiver 38 for transferring the recovered metal-containing residue to the biomass receiver 11. A metal-containing residue supply amount regulator 82 is connected to the metal-containing residue supply equipment 37 and is configured to adjust the amount of metal-containing residue supplied to the biomass receiver 11.

[0099] Next, we will explain the C2-C4 olefin manufacturing facility 50 (hereinafter also referred to as the olefin manufacturing facility) which produces olefins with 2-4 carbon atoms from reformed gas. The composite catalyst 63 described above is placed inside the olefin manufacturing equipment 50 and is configured to come into contact with the reformed gas introduced inside. The olefin manufacturing equipment 50 is also equipped with an internal cooling device 56 to adjust the internal temperature to a temperature suitable for the reaction. The composite catalyst 63 is supplied from a catalyst mixer 57, which prepares the composite catalyst 63 by mixing methanol synthesis catalyst 58 and mesopore catalyst 59, to the olefin manufacturing equipment 50 via a catalyst mixture regulator 95 and composite catalyst supply piping 62.

[0100] The olefin manufacturing equipment 50 is configured to transfer the olefins generated as a result of the reaction inside to the oligomerization reaction equipment 42 via a distillation separator 52. The distillation separator 52 is connected to a reaction gas piping 77 that transfers the gas containing carbon monoxide and methane separated from the olefin to the shift reaction hydrogen production equipment 53.

[0101] Next, we will describe the oligomerization reaction equipment used to produce iso-oligomers with 6 to 16 carbon atoms by oligomerizing olefins with 2 to 4 carbon atoms. The oligomerization reaction equipment 42, as an oligomerization reaction facility, is configured to oligomerize olefins introduced into it via C2-C4 olefin piping 47 to produce iso-oligomers having 6 to 16 carbon atoms. The oligomerization reaction apparatus 42 houses the oligomerization catalyst described above, and is equipped with a heating and pressurizing device that can adjust the temperature and pressure to be appropriate for the oligomerization reaction. The oligomerization reaction equipment 42 is connected to C6-C16 iso-oligomer piping 48, which transfers the iso-oligomers produced by the reaction to the hydrogenation equipment 44 via a distillation purification unit 43.

[0102] Next, we will describe a hydrogenation facility 44 that hydrogenates isooligomers to produce isoparaffins and then hydrogenates them to produce biojet fuel containing the isoparaffins. The hydrogenation equipment 44 houses the hydrogenation catalyst described above, and is equipped with a heating and pressurizing device that can adjust the temperature and pressure to be appropriate for the hydrogenation reaction. In the hydrogenation plant 44, bio-jet fuel 90 consisting of C6-C16 isoparaffins is obtained and discharged from the C6-C16 isoparaffin piping 49.

[0103] (Equipment for hydrogen and carbon dioxide recycling) This section describes the equipment used in the manufacturing apparatus of this embodiment for circulating hydrogen and carbon dioxide generated during the production of bio-jet fuel. The bio-jet fuel production apparatus 100 of this embodiment further comprises a shift reaction hydrogen production apparatus 53 that generates hydrogen and carbon dioxide by reacting carbon monoxide and methane in the reaction gas generated in the olefin production apparatus 50 with water vapor. Including such a shift reaction hydrogen production apparatus 53 is optional. The shift reaction hydrogen production facility 53 is configured to introduce a light gas containing carbon monoxide and methane, which has been separated from C2-C4 olefins in the distillation separator 52 from the reaction gas discharged from the olefin production facility 50, into the shift reaction hydrogen production facility 53 via the distillation separator 52. Inside the shift reaction hydrogen production facility 53, a shift reaction hydrogenation catalyst is arranged and configured to generate a mixed gas containing hydrogen and carbon dioxide through the shift reaction described above. The shift reaction hydrogen production equipment 53 is connected to an H2 / CO2 gas pipeline 64 that transfers the generated mixed gas to the gas separation and purification equipment 54.

[0104] The gas separation and purification equipment 54 is equipped with a CO2 supply pipe 32 to separate CO2 from the mixed gas generated in the shift reaction hydrogen production equipment 53 and introduce it to the reforming gasifier 30 via a CO2 supply regulator 83. Separation devices such as a PSA (Pressure Swing Adsorption) type gas separator and a ceramic membrane type gas separator are used as the gas separation and purification equipment 54.

[0105] The hydrogen separated in the gas separation and purification equipment 54 is transferred to the hydrogen holder 55 via the hydrogen supply piping 79. The hydrogen holder 55 is connected to the gas mixing and preparing equipment 89 and the water electrolysis equipment 40. The water electrolysis equipment 40 generates hydrogen by electrolyzing tap water 4. The hydrogen generated in the water electrolysis equipment 40 is transferred to the hydrogen holder 55 via the hydrogen supply pipe 51 and the water electrolysis hydrogen supply amount regulator 87, and hydrogen is supplied to the gas mixing regulator 89 via the hydrogen supply pipe 78 to adjust the H2 / CO gas ratio in the reformed gas. This configuration is designed to increase the volume ratio of H2 / CO in the reformed gas.

[0106] (Equipment for circulating exhaust heat gases) Next, we will describe the equipment used for circulating the waste heat gas, which is provided to utilize the heat generated in the manufacturing apparatus of this embodiment in each process. In the bio-jet fuel production apparatus 100 of this embodiment, multiple combustion gas pipes are provided to utilize the heat generated in each process as waste heat gas for heating within the apparatus. The multiple combustion gas pipes in this embodiment consist of pipes that transport the combustion gas 6 generated by the air fuel furnace 60, which burns the carbonization gas discharged from the carbonization furnace 20, to each device. Examples of such multiple combustion gas pipes include a combustion gas pipe 71 that supplies combustion gas to the dryer 12 via a combustion gas pipe 70 connected to the air fuel furnace 60 and a combustion gas flow regulator 61, a combustion gas pipe 72 that supplies to the carbonization furnace, a combustion gas pipe 73 that supplies to the reforming gasifier 30, a combustion gas pipe 75 that supplies to the olefin manufacturing equipment 50, a combustion gas pipe 96 that supplies to the oligomerization reactor, a combustion gas pipe 97 that supplies to the hydrogenation reactor, and a combustion gas pipe 76 that supplies to the shift reaction hydrogen manufacturing equipment 53. The system also includes combustion gas piping 74 that supplies the combustion gas generated in the reforming gasification furnace 30 to the steam heat exchanger 31. By transferring the combustion gas to each device, the high-temperature gas generated in the apparatus 100 of this embodiment can be recycled and used for heating in each device.

[0107] The method for producing bio-jet fuel using the bio-jet fuel production apparatus 100 of this embodiment may be the method described in the production methods of the first and second embodiments above. Furthermore, the production method may use all of the functions of the production apparatus 100 of this embodiment, or it may use only some of them. In other words, the embodiments of the production method and the embodiments of the production apparatus are shown as independent and separate embodiments.

[0108] The bio-jet fuel manufacturing method and apparatus according to this embodiment are as described above, but the embodiments disclosed herein should be considered in all respects to be illustrative and not restrictive. The scope of the present invention is indicated by the claims rather than the foregoing description, and all modifications within the meaning and scope equivalent to the claims are intended to be included. [Examples]

[0109] Next, embodiments of the present invention will be described together with comparative examples. However, the present invention is not limited to the embodiments described below.

[0110] (Test 1) We conducted a test to produce jet fuel using a bio-jet fuel production apparatus with the configuration shown in Figure 1. In this experiment, sewage sludge and organic waste were fed into a dryer and a carbonizer as biomass. Carbonization was carried out in the carbonizer, a reforming and gasification reaction was carried out in a reforming and gasification furnace, a shift reaction and methane reforming reaction were carried out in a shift reaction hydrogen production facility, and gas separation and purification was carried out in a PSA type gas separation and purification unit. The recovered hydrogen was supplied to the reformed gas to adjust the reformed gas composition to H2 / CO = 2.5 (volume ratio). The carbon dioxide separated by the gas separation device was recycled and supplied to the reforming gasification furnace. The metal-containing residue separated and recovered by the cyclone dust collector was recycled and supplied to a dryer for sewage sludge and organic waste. The experimental results for the carbonization rate, reformed gas production amount, gas composition (volume %), and bio-jet fuel production amount when the metal-containing residue is recycled and supplied to sewage sludge and organic waste, and when it is not, are shown in Example 1 and Comparative Example 1.

[0111] The specific testing method is as follows: Sewage sludge (80% by mass moisture content) was fed in at a rate of 30 kg per hour. Construction waste chips were fed in at a rate of 10 kg per hour as organic waste. Carbonization was carried out under conditions of carbonization furnace temperature of 250-450°C. Reform gasification was carried out under conditions of steam / carbide (mass ratio) = 1.5, CO2 / carbide (molar ratio) = 0.5, and temperature of 860°C. The shift reaction hydrogen production process was carried out under conditions of temperature of 450°C and pressure of 3.5 MPa under a shift reaction hydrogen production catalyst prepared by supporting Fe, Ru, Ni, Cu, Zn, Mg, Zr, Ti, and Ce on porous oxide. Metal-containing residue separated and recovered by a cyclone dust collector was fed into a kiln-type dryer at a rate of 3 kg per hour, which mixed and treated the sewage sludge and construction waste chips. In this study, the olefin production process using reformed gas was carried out using a composite catalyst prepared by mixing a methanol synthesis catalyst (Cu / ZnO) and a mesopore catalyst (SAPO-34). The reaction conditions were 380°C and 2.5 MPa. The oligomerization reaction of olefins was carried out under reaction conditions of 120-250°C and 2.5-5 MPa. Hydrogenation after the oligomerization reaction was carried out under reaction conditions of 0.1–2.5 MPa and 250–450°C. The composition of the reformed gas components and the concentrations of CO, hydrogen, CO2, CH4 and other components in the outlet gas of the shift reaction hydrogen production apparatus were measured using a thermal conductivity type gas chromatograph analyzer (GC-14B manufactured by Shimadzu Corporation) filled with Gaskuropack and molecular sieve 13X and an FID gas chromatograph analyzer (GC-8A manufactured by Shimadzu Corporation). The flow rate of the exhaust gas was measured with a wet gas flow meter. The content of metal elements in the metal-containing residue was measured with an ICP emission spectroscopic analyzer (ICPS-8100 manufactured by Shimadzu Corporation) and a fluorescent X-ray analyzer (EA1400 manufactured by Hitachi High-Tech Corporation). The metal content of the metal-containing residue obtained in this test is Na 35 g / kg, K 85 g / kg, Ca 46 g / kg, Mg 27 g / kg, Ba 5 g / kg, Fe 7.5 g / kg and Ni 3.8 g / kg. The yield of biojet fuel in the table indicates the weight (per hour) of the liquid oil composed of C6-C16 isoparaffins obtained after hydrogenation. The results are shown in Table 1.

[0112]

Table 1

[0113] From these results, regarding the production amount (Nm 3 / h) of the reformed gas using sewage sludge and construction waste as raw materials and the production amount (kg / h) of biojet fuel composed of C6-C16 isoparaffins, it was shown that when the metal-containing residue was recycled and supplied (Example 1), it was significantly improved compared to the case where it was not recycled and supplied (Comparative Example 1).

[0114] (Test 2) Using sewage sludge and rice straw of agricultural waste as biomass, tests of carbonization, reformed gasification and biojet fuel production similar to Test 1 were conducted. Sewage sludge (80% moisture content) was fed in at a rate of 45 kg per hour. Rice straw was fed in at a rate of 20 kg per hour as organic waste. The carbonization operation was carried out under conditions of carbonization furnace temperature of 250 to 420°C. Table 2 shows the amount of reformed gas produced, the composition of the reformed gas components, and the amount of bio-jet fuel produced in Example 2, which was carried out at a temperature of 900°C under conditions of mixed supply of steam and CO2 with a steam / carbonized material (mass ratio) of 1.7 and CO2 / carbonized material (molar ratio) of 0.35, and in Comparative Example 2, which was carried out under conditions of supplying only steam with a steam / carbonized material ratio of 1.7.

[0115] The shift reaction hydrogen production process was carried out under a composite catalyst consisting of Ru, Cu, Cr, K, Li, La, and Nd supported on a porous oxide, at a temperature of 350°C and a pressure of 0.3 MPa. In the olefin production process using reformed gas in this test, the reaction conditions for the olefin production process, which uses a composite catalyst consisting of a methanol synthesis catalyst (Cu-Pd / ZnO) and a mesopore catalyst (ZMS-11), were 380°C and 2.5 MPa. The oligomerization reaction of olefins was carried out under reaction conditions of 120-250°C and 2.5-5 MPa. Hydrogenation after the oligomerization reaction was carried out under reaction conditions of 0.1-2.5 MPa and 250-450°C. The metal-containing residue separated and recovered by the cyclone dust collector was mixed and fed into a dryer for sewage sludge and rice straw raw materials at a rate of 5 kg per hour for carbonization. The metal content of the metal-containing residue obtained in this test is as follows: Na 23 g / kg, K 65 g / kg, Ca 50 g / kg, Mg 15 g / kg, Ba 2.5 g / kg, Li 0.5 g / kg, Fe 8.2 g / kg, and Ni 2.5 g / kg. The results are shown in Table 2.

[0116] [Table 2]

[0117] From these results, it can be seen that in the reforming and gasification process of carbonized materials using sewage sludge and rice straw as raw materials, the reformed gas (Nm³) under the mixed supply conditions of steam and CO2 (Example 2) 3 The production volume (kg / h) of bio-jet fuel and the amount of water vapor supplied alone were shown to increase significantly compared to the water vapor-only supply condition (Comparative Example 2). [Industrial applicability]

[0118] In the present invention, in a biomass carbonization process, a method for producing reformed gas and bio-jet fuel, and a bio-jet fuel production apparatus, the production efficiency of reformed gas and bio-jet fuel can be improved by recycling the metal-containing residue from the reformed gasification process into biomass, and by recycling the carbon dioxide emitted in the shift reaction hydrogen production process into the reformed gasifier. As a result, it becomes possible to reduce the production cost of bio-jet fuel and reduce the environmental burden based on the reduction of carbon dioxide emissions. [Explanation of symbols]

[0119] 1. Biomass (sewage sludge, organic waste) 2. Carbides 3 Metal-containing residue 4 Water supply 5. Drying gas (containing tar) 6. Combustion gases 7. Water vapor 8. Reformed gas 9 CO2 10 Hydrogen 11. Biomass receiver 12 Rotary Kiln Dryer 20 Carbonization furnace 30 Reforming Gasifier 31. Steam heat exchanger 32 CO2 supply piping 33 Steam supply piping 34. Dust collector (cyclone) 35. Modified gas piping 36 Gas Purifier 37 Metal-containing residue supply equipment 38 Metal-containing residue receiver 39 Metal-containing residue discharge piping 40 Water electrolysis equipment 41 Air blower 42. Oligomerization reaction equipment 43 Distillation and purification apparatus 44 Hydrogenation Equipment 45. Light Olefin Recycling Piping 46 C2-C4 Olefins 47 C2~C4 Olefin Piping 48 C6~C16 Iso-Oligomer Piping 49 C6~C16 Isoparaffin Piping 50 C2-C4 Olefin Manufacturing Facilities 51. Hydrogen supply piping (hydrogen from water electrolysis) 52 Distillation Separator 53 Shift Reaction Hydrogen Production Equipment 54. Gas separation and purification equipment (ceramic membrane separator, PSA) 55 Hydrogen holder 56 Internal cooling system 57 Catalyst Mixing Preparator 58 Methanol synthesis catalyst 59 Mesopore Catalyst 60 Air Combustion Furnaces 61 Combustion gas flow regulator 62 Composite catalyst supply piping 63. Compound catalyst 64 H2 / CO2 gas piping 70 Combustion gas piping 71. Combustion gas piping (dryer) 72 Combustion gas piping (carbonization furnace) 73 Combustion gas piping (reformed gasification furnace) 74. Combustion gas piping (steam heat exchanger) 75. Combustion gas piping (for C2-C4 olefin manufacturing facilities) 76. Combustion gas piping (shift reaction hydrogen production equipment) 77 Reaction gas piping 78. Hydrogen supply piping (gas separation and purification unit) 79. Hydrogen supply piping (hydrogen holder) 80. Biomass supply adjustment means 81. Carbide supply regulator 82 Metal-containing residue supply amount regulator 83 CO2 supply amount regulator 84. Steam supply regulator 85 Hydrogen supply regulator 86. Reformed gas supply rate regulator 87 Water electrolysis hydrogen supply amount regulator 88. Booster gas circulation equipment 89 Gas Mixing and Adjusting Device 90. Bio-jet fuel (C6-C16 isoparaffin) 91 Biomass supply facilities 92 Carbide supply device 93 Reformed gas supply device 94 Metal-containing residue separation and recovery equipment 95 Catalyst mixture amount regulator 96 Combustion gas piping (oligomerization reaction equipment) 97 Combustion gas piping (hydrogenation reactor) 100 Jet fuel manufacturing equipment

Claims

1. The carbonization process involves carbonizing biomass to produce carbonized material, A reforming gasification step involves reacting the aforementioned carbide with water vapor and carbon dioxide to produce a reformed gas containing hydrogen, carbon monoxide, methane, and carbon dioxide. An olefin production process in which the reformed gas is brought into contact with a methanol synthesis catalyst and a mesopore catalyst to produce olefins having 2 to 4 carbon atoms, An oligomerization reaction step to produce an isooligomer having 6 to 16 carbon atoms by oligomerizing the aforementioned olefin, A hydrogenation step to hydrogenate the isooligomer to produce isoparaffin and to produce biojet fuel containing the isoparaffin, A method for producing biojet fuel, comprising a separation and recovery step of separating and recovering a metal-containing residue generated together with the reformed gas in the reformed gasification step, and mixing the recovered metal-containing residue with the biomass.

2. The method for producing bio-jet fuel according to claim 1, wherein the metal-containing residue comprises at least one element selected from the group consisting of alkali metals and alkaline earth metals including sodium, potassium, lithium, calcium, magnesium, and barium, boron, aluminum, iron, and nickel.

3. The method for producing bio-jet fuel according to claim 1 or 2, wherein the olefin production step comprises a separation step of separating the reaction gas generated by contacting the reformed gas with a methanol synthesis catalyst and a mesopore catalyst into a mixed gas containing carbon monoxide and methane and an olefin having 2 to 4 carbon atoms.

4. A method for producing biojet fuel according to claim 1 or 2, further comprising a shift reaction hydrogen production step in which carbon monoxide and methane in the reaction gas generated in the olefin production step are reacted with water vapor to produce hydrogen and carbon dioxide.

5. A method for producing bio-jet fuel according to claim 4, comprising introducing carbon dioxide generated in the shift reaction hydrogen production step into the reforming gasification step, and mixing the hydrogen generated in the shift reaction hydrogen production step with the reformed gas obtained from the reforming gasification step.

6. A method for producing bio-jet fuel according to claim 4, wherein in the shift reaction hydrogen production step, a shift reaction catalyst is used which comprises at least one element selected from the group consisting of iron, ruthenium, nickel, copper, zinc, potassium, lithium, magnesium, chromium, cobalt, molybdenum, zirconia, titanium, cerium, lanthanum, and neodymium, and a porous oxide support.

7. A method for producing bio-jet fuel according to claim 1 or 2, wherein the carbonization gas generated together with the carbide in the carbonization step is burned and introduced into at least one of the steps of the carbonization step, the reforming gasification step, the steam heat exchange step, the olefin production step, and the oligomerization reaction step.

8. A method for producing bio-jet fuel according to claim 4, wherein the carbonization gas generated together with the carbide in the carbonization step is burned and introduced into at least one of the following steps: the carbonization step, the reforming gasification step, the steam heat exchange step, the shift reaction hydrogen production step, the olefin production step, and the oligomerization reaction step.

9. A method for producing bio-jet fuel according to claim 1 or 2, wherein the methanol synthesis catalyst comprises at least one element selected from the group consisting of copper, zinc, chromium, manganese, scandium, lithium, sodium, potassium, cesium, magnesium, barium, platinum, palladium, iridium, molybdenum, tungsten, vanadium, zirconium, hafnium, titanium, yttrium, cerium, and lanthanum, and a porous carrier.

10. The method for producing bio-jet fuel according to claim 1 or 2, wherein the mesoporous catalyst comprises a porous carrier made of a mesoporous zeolite and a mesoporous clay mineral.

11. The method for producing bio-jet fuel according to claim 1 or 2, wherein in the olefin production step, a composite catalyst prepared by mixing the methanol synthesis catalyst and the mesopore catalyst is used, and the volume ratio of the methanol synthesis catalyst to the mesopore catalyst in the methanol synthesis catalyst is 0.1 to 5.

12. A carbonization furnace that introduces biomass to produce carbonized material, A reforming gasifier is provided, which introduces the carbides obtained in the aforementioned carbonization furnace and reacts them with steam and carbon dioxide to produce a reformed gas containing hydrogen, carbon monoxide, methane, and carbon dioxide. An olefin production facility that introduces the reformed gas obtained in the reforming gasification furnace and brings it into contact with a methanol synthesis catalyst and a mesopore catalyst to produce olefins having 2 to 4 carbon atoms, An oligomerization reaction apparatus for introducing the aforementioned olefin and carrying out an oligomerization reaction to produce isoparaffins having 6 to 16 carbon atoms, The facility includes a hydrogenation plant that introduces isoparaffin obtained in the oligomerization reaction plant and hydrogenates it to obtain biojet fuel, A separation and recovery means for separating and recovering metal-containing residue generated together with the reformed gas in the reformed gasification furnace, A bio-jet fuel production apparatus comprising means for introducing the metal-containing residue recovered by the separation and recovery means into the biomass.

13. The bio-jet fuel production apparatus according to claim 12, further comprising a shift reaction facility that reacts carbon monoxide and methane in the reaction gas generated in the olefin production facility with water vapor to produce hydrogen and carbon dioxide.

14. The bio-jet fuel production apparatus according to claim 12 or 13, further comprising separation means for separating the generated reaction gas into an olefin having 2 to 4 carbon atoms and a gas containing carbon monoxide and methane.

15. The bio-jet fuel production apparatus according to claim 13, wherein the shift reaction equipment is provided with a transfer means for transferring the generated carbon dioxide to the reforming gasification furnace.

16. The system includes a combustion device for burning the carbonization gas discharged from the carbonization furnace. The bio-jet fuel production apparatus according to claim 12, further comprising a supply means for supplying the burned gas as a heating gas to at least one of the carbonization furnace, the reforming gasification furnace, the olefin production equipment, the oligomerization reaction equipment, and the hydrogenation equipment.

17. The system includes a combustion device for burning the carbonization gas discharged from the carbonization furnace. The bio-jet fuel production apparatus according to claim 13, further comprising a supply means for supplying the combusted gas as a heating gas to at least one of the carbonization furnace, the reforming gasification furnace, the olefin production equipment, the oligomerization reaction equipment, the hydrogenation equipment, and the shift reaction equipment.

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